US20190093226A1 - Method for applying a pecvd lubricity layer with a moving gas inlet - Google Patents

Method for applying a pecvd lubricity layer with a moving gas inlet Download PDF

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Publication number
US20190093226A1
US20190093226A1 US16/092,124 US201716092124A US2019093226A1 US 20190093226 A1 US20190093226 A1 US 20190093226A1 US 201716092124 A US201716092124 A US 201716092124A US 2019093226 A1 US2019093226 A1 US 2019093226A1
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coating
vessel
layer
pecvd
lubricity
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James Newton
Brian Russell Lilly
Becky L. Clark
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Sio2 Medical Products LLC
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SIO2 Medical Products Inc
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Assigned to OAKTREE FUND ADMINISTRATION, LLC reassignment OAKTREE FUND ADMINISTRATION, LLC SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SIO2 MEDICAL PRODUCTS, LLC
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • C23C16/507—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using external electrodes, e.g. in tunnel type reactors
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/178—Syringes
    • A61M5/31—Details
    • A61M5/3129—Syringe barrels
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36—Carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45587—Mechanical means for changing the gas flow
    • C23C16/45589—Movable means, e.g. fans
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/178—Syringes
    • A61M5/31—Details
    • A61M5/3129—Syringe barrels
    • A61M2005/3131—Syringe barrels specially adapted for improving sealing or sliding
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2205/00—General characteristics of the apparatus
    • A61M2205/02—General characteristics of the apparatus characterised by a particular materials
    • A61M2205/0222—Materials for reducing friction
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2205/00—General characteristics of the apparatus
    • A61M2205/02—General characteristics of the apparatus characterised by a particular materials
    • A61M2205/0238—General characteristics of the apparatus characterised by a particular materials the material being a coating or protective layer
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2207/00—Methods of manufacture, assembly or production
    • A61M2207/10—Device therefor

Definitions

  • the present invention relates to the technical field of fabrication of a surface (e.g. an interior surface of a syringe barrel, an exterior surface of a needle or a plunger), a plastic article, an object, a vessel, or a medical device part, having a lubricity coating applied by plasma enhanced chemical vapor deposition (PECVD).
  • PECVD plasma enhanced chemical vapor deposition
  • the invention also relates to fabrication of coated surface with an advantage of combination of high lubricity (e.g. low and consistent plunger force) and low particle count.
  • the invention further relates to methods of applying a PECVD lubricity layer or coating to a surface, a plastic article, a vessel, a medical device part.
  • the invention relates to a coating method providing relative movement between a gas inlet and a coated substrate, when applying a lubricity layer to the surface of the substrate, using PECVD.
  • the invention further relates to a two-phase coating method including a PECVD lubricity coating deposition applied using a first electromagnetic power at the first phase, followed by a crosslinking using a second electromagnetic power at the second phase, wherein the power level of the second power is higher than the power level of the first power.
  • a lubricant either on one or on both of the barrel and the plunger, is desirable.
  • vessels which have to be closed by a stopper, and to the stopper itself, and more generally to any surface which should provide a certain lubricity, for example, the exterior surface of a needle.
  • lubrication is traditionally applied to the barrel-contacting engagement surface of the plunger, the interior surface of the barrel, or both.
  • Liquid or gel-like oily lubricants such as free silicone oil (e.g., polydimethylsiloxane or “PDMS”), may provide a desired level of lubrication between the plunger and the barrel to optimize plunger force.
  • PDMS is, in fact, a standard oily lubricant used in the industry.
  • oily lubricant can mix and interact with the drug product in a vessel and they tend to generate more particulates or sub visible particulates which may also interact with the drug product held by the container.
  • the oily lubricant and/or the particulates they generate can potentially degrade the drug or otherwise affect its efficacy and/or safety. Degradation is particularly an issue in the case of protein compositions and polypeptide compositions, which occupy a market with tremendous growth potential. Further, such lubricants may in some cases be problematic if they are injected into the patient along with the drug product.
  • Prefilled syringes are commonly prepared and sold so the syringe does not need to be filled before use.
  • the syringes can be prefilled with saline solution, a dye for injection, or a pharmaceutically active preparation, for some examples.
  • the silicon oil particulates may migrate away from the plunger over time, resulting in spots between the plunger and the interior surface of the container with little or no lubrication. This may cause a phenomenon known as “stiction,” an industry term for the adhesion between the plunger and the barrel that needs to be overcome to break out the plunger and allow it to begin moving.
  • U.S. Pat. No. 7,985,188 and EP2796591A1 which is incorporated herein by reference in its entirety, discloses methods and apparatuses for applying a lubricity layer to plastic containers using plasma enhanced chemical vapor deposition (“PECVD”).
  • PECVD plasma enhanced chemical vapor deposition
  • the method disclosed in that patent involves feeding a monomer into a vessel with a gas inlet tube when performing PECVD.
  • the gas inlet tube according to methods disclosed in that patent, is stationary during PECVD.
  • the present invention pertains to plastic vessels and medical devices, in particular vials and syringes, coated with PECVD coatings made from organosilicon precursors with further treatment.
  • PECVD coatings made from organosilicon precursors with further treatment.
  • a plasma coating SiO x C y H z or its equivalent Si w O x C y H z , in which x is from about 0.5 to about 2.4 as measured by X-ray photoelectron spectroscopy (XPS), y is from about 0.6 to about 3 as measured by XPS, and z is from about 2 to about 9 as measured by at least one of Rutherford backscattering spectrometry (RBS) or hydrogen forward scattering (HFS)) is provided.
  • This plasma coating improves lubricity (“lubricity coating”), thus eliminating the need for traditional silicon oil lubricants e.g. in syringes.
  • Further embodiments of the invention are methods to achieve high lubricity, low particle counts or combination of both by said coatings and the resulting coated devices.
  • the inventors have found that providing relative motion between the vessel and the gas inlet tube during PECVD provides high lubricity throughout the inner walls of the vessel and high electromagnetic power reduces sub-visible particulates from the lubricity layer in the vessel's liquid contents.
  • a method for applying a lubricity layer to a surface of a vessel with a two-phase PECVD process.
  • the lubricity layer is applied to an inner surface of a vessel, such as a generally tubular vessel.
  • the method includes providing a vessel, such as the generally tubular vessel, to be processed.
  • the vessel may include an inner surface defining a lumen and an opening at an end of the vessel providing access to the lumen or an object to be processed including an outer surface.
  • a gas inlet having an internal passage having at least one outlet is provided.
  • An outer electrode is provided.
  • a gaseous PECVD precursor is introduced into the lumen via at least one outlet of the internal passage.
  • Electromagnetic energy is applied to the outer electrode under conditions effective to form a PECVD lubricity layer on at least a portion of the inner surface of the vessel.
  • Relative axial motion between the vessel and the gas inlet is provided during at least some time when electromagnetic energy is applied to the outer electrode during the PECVD lubricity coating process, optionally at the first phase, or at the second phase or both.
  • the PECVD lubricity coating deposited during the first phase is crosslinked with higher power level of electromagnetic energy than the power level of the electromagnetic energy applied at the first phase.
  • the invention particularly relates to the PECVD lubricity coating process wherein the plasma-forming energy is applied at a first phase at a first energy level followed by a further treatment at a second phase at a second energy level higher than the first energy level.
  • the invention particularly relates to a PECVD lubricity coating process which generates a lubricity coating with the advantage of a combination of consistent low plunger force and low sub-visible particle count.
  • the invention further pertains to a substrate coated with the product of the above method, to a vessel processing system for coating of a vessel, the system comprising a processing station arrangement configured for performing the above and/or below mentioned method steps.
  • the invention further pertains to a computer-readable medium, in which a computer program for coating of a vessel is stored which, when being executed by a processor of a vessel processing system, is adapted to instruct the processor to control the vessel processing system such that it carries out the above and/or below mentioned method steps.
  • the invention further pertains to a program element or computer program for coating of a vessel, which, when being executed by a processor of a vessel processing system, is adapted to instruct the processor to control the vessel processing system such that it carries out the above and/or below mentioned method steps.
  • the processor may thus be equipped to carry out exemplary embodiments of the methods of the present invention.
  • the computer program may be written in any suitable programming language, for example, C++ and may be stored on the computer-readable medium, such as a CD-ROM. Also, the computer program may be available from a network, such as the Worldwide Web, from which it may be downloaded into image processing units or processors, or any suitable computers.
  • the current invention addresses the long-standing shortcomings of conventional silicone oil lubricant and the PECVD lubricity coatings currently in the art on parenteral syringes and cartridges. Specifically, a combination of consistent low plunger force and low sub-visible particle count is enabled by this invention through at least moving inlet and a post-deposition higher power crosslinking treatment.
  • the subject invention preferably addresses those needs, and others.
  • coating methods and the coated devices resulting from the methods are described.
  • the methods can be carried out on the equipment (vessel processing system and vessel holder) which is also described below or in U.S. Pat. No. 7,985,188 and EP2796591A1, each of which is incorporated by reference herein in its entirety and for all purposes.
  • FIG. 1 is a schematic sectional view of a vessel holder in a coating station according to an embodiment of the disclosure.
  • FIG. 2 is a section taken along section lines A-A of FIG. 1 .
  • FIG. 3 is a graph illustrating the effect of a moving gas inlet on high power OMCTS coating.
  • FIG. 4 is a graph illustrating the plunger force achieved with Process 1.
  • FIG. 5 is a graph illustrating the plunger force achieved with Process 2.
  • FIG. 6 is a graph illustrating the plunger force achieved with Process 3.
  • FIG. 7 is a graph illustrating the plunger force achieved with Process 4.
  • FIG. 8 is a graph illustrating the particle count in each size category achieved with Process 3.
  • FIG. 9 is a graph illustrating the particle count in each size category achieved with Process 4.
  • FIG. 10 shows the FT-IR spectrum for lubricity coating applied by Process 4.
  • FIGS. 11A and 11B show isometric and front views, respectively, of an exemplary holder (located at least partially within a coating chamber) useful to coat an outer surface of a vessel or an object, in accordance with at least one embodiment of the present invention.
  • FIG. 12 is a schematic sectional view of a syringe showing a coating set prepared on the substrate before a lubricity coating is applied according to an exemplary embodiment of the present invention.
  • FIG. 12A shows an enlarged detail view of the syringe barrel wall of FIG. 12 .
  • FIG. 13 is a schematic sectional view of a syringe showing a barrier coating prepared on the substrate before a lubricity coating is applied according to an exemplary embodiment of the present invention.
  • FIG. 13A shows an enlarged detail view of the syringe barrel wall of FIG. 13 .
  • FIG. 14 is a schematic sectional view of a syringe showing a schematic representation of a bilayer coating set (i.e. a tie layer and a barrier coating) prepared on the substrate before a lubricity coating is applied according to an exemplary embodiment of the present invention.
  • a bilayer coating set i.e. a tie layer and a barrier coating
  • FIG. 14A shows an enlarged detail view of the syringe barrel wall of FIG. 14 .
  • FIG. 15 is a schematic sectional view of a syringe showing a trilayer coating set (i.e. a tie layer, a barrier coating and a pH protective coating) prepared on the substrate before a lubricity coating is applied according to an exemplary embodiment of the present invention.
  • a trilayer coating set i.e. a tie layer, a barrier coating and a pH protective coating
  • FIG. 15A shows an enlarged detail view of the syringe barrel wall of FIG. 15 .
  • FIG. 16 is a schematic sectional view of a syringe showing a lubricity coating applied on a polymer substrate surface.
  • FIG. 16A shows an enlarged detail view of the syringe barrel wall of FIG. 16 .
  • FIG. 17 is a schematic sectional view of a syringe showing a lubricity coating applied on a glass surface.
  • FIG. 17A shows an enlarged detail view of the syringe barrel wall of FIG. 17 .
  • FIG. 18 is a sectional view of a syringe showing an exemplary depth of plunger insertion for plunger force testing.
  • Vessel processing system 50 Vessel holder 70 Conveyor 80 Vessel 82 Opening 84 Closed end 86 Wall 88 Interior surface 90 Coating(s) 92 Vessel port 94 Vacuum duct 96 Vacuum port 98 Vacuum source 100 O-ring (of 92) 102 O-ring (of 96) 104 Gas inlet port 106 O-ring (of 100) 108 Probe (inner electrode) 110 Gas delivery port (of 108) 114 Housing (of 50) 116 Collar 118 Exterior surface 144 PECVD gas source 160 Outer electrode 162 Power supply 164 Sidewall (of 160) 166 Sidewall (of 160) 168 Closed end (of 160) 250 Syringe barrel 252 Syringe 254 Interior surface (of 250) 256 Back end (of 250) 258 Plunger (of 252) 260 Front end (of 250) 262 Cap 264 Interior surface (of 262) 268 Vessel 274 Lumen 280 Polymer surface 282 Tie layer 284 pH protective layer 285 Underlying layer(s) 2
  • a wide variety of different containers, vessels, or surfaces can be treated according to any embodiment.
  • the terms “container” and “vessel” as used throughout this specification may be any type of article that is adapted to contain or convey a substrate.
  • the substrate can be a liquid, a gas, a solid, or any two or more of these.
  • a container or vessel is an article with at least one opening (e.g., one, two or more, depending on the application) and a wall defining an interior contacting surface.
  • a surface is a vessel lumen surface, where the vessel is, for example, a vial, a tube, a bottle, ajar, a syringe, a cartridge, a blister package, a flexible package, or an ampoule.
  • the surface of the material can be a fluid surface of an article of labware, for example a microplate, a centrifuge tube, a pipette tip, a well plate, a microwell plate, an ELISA plate, a microtiter plate, a 96-well plate, a 384-well plate, a centrifuge tube, a chromatography vial, an evacuated blood collection tube, or a specimen tube, which are several non-limiting examples.
  • the term “vessel” is used herein for simplicity to mean a container, a vessel, or a surface, unless otherwise specifically detailed in the appropriate context.
  • a vessel can be of any shape, a vessel having a substantially cylindrical wall adjacent to at least one of its open ends being preferred. Though the invention is not necessarily limited to vessels of a particular volume, vessels are contemplated in which the lumen has a void volume of from 0.5 to 50 mL, optionally from 1 to 10 mL, optionally from 0.5 to 5 mL, optionally from 1 to 3 mL.
  • the substrate surface can be part or all of the inner surface of a vessel having at least one opening and an inner surface.
  • the interior wall of the vessel is cylindrically shaped, like, e.g. in a sample tube or a syringe barrel. Sample tubes and syringes or cartridges or their parts (for example syringe or cartridge barrels) are contemplated.
  • An object can be of any shape with an outer surface to be processed.
  • the object can be a part of a medical device, for example, a piston, a plunger or a needle.
  • the object can also be a vessel.
  • an object holder is utilized.
  • Crosslink is a bond formed between polymer chains. “Crosslinking” in the context of the present invention refers to any treatment uses crosslinks to modify the properties of the coating.
  • a “lubricity layer” or “lubricity coating” or any similar term is generally defined as a coating that reduces the frictional resistance of the coated surface, relative to the uncoated surface. In other words, it reduces the frictional resistance of the coated surface in comparison to a reference surface which is uncoated.
  • the present lubricity layers are primarily defined by their lower frictional resistance than the uncoated surface and the process conditions providing lower frictional resistance than the uncoated surface.
  • the lubricity coating has a composition according to the empirical composition or sum formula Si w O x C y H z .
  • the atomic ratio can be determined by XPS (X-ray photoelectron spectroscopy).
  • the coating may thus in one aspect have the formula Si w O x C y H z , or its equivalent SiO x C y H z , for example where w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from about 2 to about 9 as measured by at least one of Rutherford backscattering spectrometry (RBS) and hydrogen forward scattering spectrometry (HFS), preferably RBS.
  • RBS Rutherford backscattering spectrometry
  • HFS hydrogen forward scattering spectrometry
  • w, x, y, and z used throughout this specification should be understood as ratios or an empirical formula (e.g. for a coating), rather than as a limit on the number or type of atoms in a molecule.
  • octamethylcyclotetrasiloxane which has the molecular composition Si 4 O 4 C 8 H 24
  • Si 4 O 4 C 8 H 24 can be described by the following empirical formula, arrived at by dividing each of w, x, y, and z in the molecular formula by 4, the largest common factor: Si 1 O 1 C 2 H 6 .
  • the values of w, x, y, and z are also not limited to integers.
  • SiO x C y H z is described as equivalent to SiO x C y , it is not necessary to show the presence of hydrogen in any proportion to show the presence of SiO x C y .
  • RF radio frequency
  • Fi refers to the force required to initiate movement of the plunger rod or plunger tip within the barrel of a syringe, cartridge or any other vessel.
  • Fm refers to the force required to maintain movement of the plunger rod or plunger tip within the barrel of a syringe, cartridge or any other vessel.
  • First and “second” or similar references to, e.g., processing stations or processing devices refer to the minimum number of processing stations or devices that are present, but do not necessarily represent the order or total number of processing stations and devices. These terms do not limit the number of processing stations or the particular processing carried out at the respective stations.
  • an “organosilicon precursor” is a compound having at least one of the linkage:
  • a volatile organosilicon precursor defined as such a precursor that can be supplied as a vapor in a PECVD apparatus, is an optional organosilicon precursor.
  • the organosilicon precursor is selected from the group consisting of a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, an alkyl trimethoxysilane, a linear silazane, a monocyclic silazane, a polycyclic silazane, a polysilsesquiazane, and a combination of any two or more of these precursors.
  • the organosilicon precursor can comprise octamethylenecyclotetrasiloxane (OMCTS), tetramethyldisiloxane (TMDSO), hexamethyldisiloxane (HMDSO), or a combination of two or more of these precursors.
  • OCTS octamethylenecyclotetrasiloxane
  • TMDSO tetramethyldisiloxane
  • HMDSO hexamethyldisiloxane
  • a model representation of the lubricant molecular structure is shown below, which is an amorphous cross-linked organosiloxane chemistry.
  • the feed amounts of PECVD precursors, gaseous reactant or process gases, and carrier gas are sometimes expressed in “standard volumes” in the specification and claims.
  • the standard volume of a charge or other fixed amount of gas is the volume the fixed amount of the gas would occupy at a standard temperature and pressure (without regard to the actual temperature and pressure of delivery).
  • Standard volumes can be measured using different units of volume, and still be within the scope of the present disclosure and claims.
  • the same fixed amount of gas could be expressed as the number of standard cubic centimeters, the number of standard cubic meters, or the number of standard cubic feet.
  • Standard volumes can also be defined using different standard temperatures and pressures, and still be within the scope of the present disclosure and claims.
  • the standard temperature might be 0° C.
  • the standard pressure might be 760 Torr (as is conventional), or the standard temperature might be 20° C. and the standard pressure might be 1 Torr. But whatever standard is used in a given case, when comparing relative amounts of two or more different gases without specifying particular parameters, the same units of volume, standard temperature, and standard pressure are to be used relative to each gas, unless otherwise indicated.
  • the corresponding feed rates of PECVD precursors, gaseous reactant or process gases, and carrier gas are expressed in standard volumes per unit of time in the specification.
  • the flow rates are expressed as standard cubic centimeters per minute, abbreviated as sccm.
  • other units of time can be used, such as seconds or hours, but consistent parameters are to be used when comparing the flow rates of two or more gases, unless otherwise indicated.
  • “Frictional resistance” can be static frictional resistance and/or kinetic frictional resistance.
  • the “plunger sliding force” (synonym to “glide force,” “maintenance force,” F m , which may also be used in this description) in the context of the present invention is the force required to maintain movement of a plunger in a syringe barrel, e.g. during aspiration or dispense. It can advantageously be determined using the ISO 7886-1:1993 test known in the art. A synonym for “plunger sliding force” often used in the art is “plunger force” or “pushing force”.
  • the “plunger breakout force” (synonym to “breakout force”, “break loose force”, “initiation force”, F i , which may also be used in this description) in the context of the present invention is the initial force required to move the plunger in a syringe, for example in a prefilled syringe.
  • Sliding force and breakout force may sometimes be used herein to describe the forces required to advance a stopper or other closure into a vessel, such as a medical sample tube or a vial, to seat the stopper in a vessel to close the vessel. Its use is analogous to use in the context of a syringe and its plunger, and the measurement of these forces for a vessel and its closure are contemplated to be analogous to the measurement of these forces for a syringe, except that at least in most cases no liquid is ejected from a vessel when advancing the closure to a seated position.
  • the plunger sliding force as defined and determined herein is suitable to determine the presence or absence and the lubricity characteristics of a lubricity layer or coating in the context of the present invention whenever the coating is applied to any syringe or syringe part, for example to the inner wall of a syringe barrel.
  • the breakout force is of particular relevance for evaluation of the coating effect on a prefilled syringe, i.e. a syringe which is filled after coating and can be stored for some time, e.g. several months or even years, before the plunger is moved again (has to be “broken out”).
  • the vessel holder 50 has a vessel port 82 configured to receive and seat the opening of a vessel 80 .
  • the interior surface of a seated vessel 80 can be processed via the vessel port 82 .
  • the vessel holder 50 can include a duct, for example a vacuum duct 94 , for withdrawing a gas from a vessel 80 seated on the vessel port 92 .
  • the vessel holder can include a second port, for example a vacuum port 96 communicating between the vacuum duct 94 and an outside source of vacuum, such as the vacuum pump 98 .
  • the vessel port 92 and vacuum port 96 can have sealing elements, for example O-ring butt seals, respectively 100 and 102 , or side seals between an inner or outer cylindrical wall of the vessel port 82 and an inner or outer cylindrical wall of the vessel 80 to receive and form a seal with the vessel 80 or outside source of vacuum 98 while allowing communication through the port. Gaskets or other sealing arrangements can or also be used.
  • FIG. 1 also illustrates that the vessel holder, for example 50 , can have a collar 116 for centering the vessel 80 when it is approaching or seated on the port 92 .
  • the vessel holder 50 comprises a gas inlet port 104 for conveying a gas into a vessel seated on the vessel port.
  • the gas inlet port 104 has a sliding seal provided by at least one O-ring 106 , or two O-rings in series, or three O-rings in series, which can seat against a cylindrical probe 108 when the probe 108 is inserted through the gas inlet port 104 .
  • the probe 108 can be a gas inlet conduit that extends to a gas delivery port at its distal end 110 .
  • the distal end 110 of the illustrated embodiment can be inserted deep into the vessel 80 for providing one or more PECVD reactants and other process gases.
  • the processing station 28 can include an electrode 160 fed by a radio frequency power supply 162 for providing an electric field for generating plasma within the vessel 80 during processing.
  • the probe 108 is also electrically conductive and is grounded, thus providing a counter-electrode within the vessel 80 .
  • the outer electrode 160 can be grounded and the probe 108 directly connected to the power supply 162 .
  • microwave power can be used to provide the electric field for generating plasma.
  • a PECVD apparatus may include a vessel holder or an object holder, an inner electrode, an outer electrode, and a power supply.
  • a vessel seated on the vessel holder defines a plasma reaction chamber, which optionally can be a vacuum chamber.
  • the object with an outer surface to be processed is placed at least partially within a chamber.
  • a source of vacuum, a reactant gas source, a gas feed or a combination of two or more of these can be supplied.
  • a gas drain not necessarily including a source of vacuum, is provided to transfer gas to or from the interior of a vessel seated on the port to define a closed chamber.
  • the PECVD apparatus can be used for atmospheric-pressure PECVD, in which case the plasma reaction chamber does not need to function as a vacuum chamber.
  • One of the optional embodiments of the present invention is a syringe part, e.g. a syringe barrel or plunger, coated with a lubricity layer.
  • a general PECVD lubricity coating method includes providing a gas including an organosilicon precursor, optionally an oxidizing gas (for example O 2 ), and an inert gas in the vicinity of the substrate surface.
  • the inert gas optionally is a noble gas, for example argon, helium, krypton, xenon, neon, or a combination of two or more of these inert gases.
  • Plasma is generated in the gas by providing plasma-forming energy adjacent to the plastic substrate.
  • PECVD plasma enhanced chemical vapor deposition
  • a drawback of some lubricity coatings in the prior art is that due to the low crosslinking nature of lubricity coating, many small spherical ‘droplets’ can be liberated from the coating on the inside of the container if it is partially filled with water and shaken.
  • the approach of the current specification to solving these issues is a lubricity layer that is chemically attached to the syringe barrel wall and moderately cross-linked to limit its mobility.
  • the lubricity coating therefore, remains stationary with no migration on the surface and minimal particle count.
  • the plunger sliding force test is a specialized test of the coefficient of sliding friction of the plunger within a syringe, accounting for the fact that the normal force associated with a coefficient of sliding friction as usually measured on a flat surface is addressed by standardizing the fit between the plunger or other sliding element and the tube or other vessel within which it slides.
  • the parallel force associated with a coefficient of sliding friction as usually measured is comparable to the plunger sliding force measured as described in this specification.
  • Plunger sliding force can be measured, for example, as provided in the ISO 7886-1:1993 test.
  • the invention involves applying a lubricity layer derived from an organosilicon precursor.
  • a lubricity layer optionally has a composition according to the empirical composition Si w O x C y or Si w N x C y , where w is 1, x is from about 0.5 to 2.4, and y is from about 0.6 to about 3.
  • the coated object is a syringe (or syringe part, e.g. syringe barrel) or any other item generally containing a plunger or movable part in sliding contact with the coated surface, the frictional resistance has two main aspects—breakout force and plunger sliding force.
  • PECVD plasma enhanced chemical vapor deposition
  • the treatment of plasma at a second phase at a second energy made occur continuously or following an interval after the first phase at a first energy level.
  • the second phase at a second energy may occur at the same apparatus, stage, or step; or at a different apparatus, stage, or step of the method and processing equipment as the first phase at a first energy level.
  • the coating characteristics are advantageously set by one or more of the following conditions: the plasma properties, the pressure under which the plasma is applied, the power applied to generate the plasma, the presence and relative amount of O 2 in the gaseous reactant, the plasma volume, and the organosilicon precursor.
  • the coating characteristics are set by the presence and relative amount of O 2 in the gaseous reactant and/or the power applied to generate the plasma.
  • the plasma is in an optional aspect hollow cathode plasma.
  • the plasma is generated at reduced pressure (as compared to the ambient or atmospheric pressure).
  • the reduced pressure is less than 300 mTorr, optionally less than 200 mTorr, even optionally less than 100 mTorr.
  • the PECVD optionally is performed by energizing the gaseous reactant containing the precursor with electrodes powered at a frequency at microwave or radio frequency, and preferably at a radio frequency.
  • the radio frequency preferred to perform an embodiment of the invention will also be addressed as “RF frequency”.
  • a typical radio frequency range for performing the present invention is a frequency of from 10 kHz to less than 300 MHz, optionally from 1 to 50 MHz, even optionally from 10 to 15 MHz.
  • a frequency of 13.56 MHz is most preferred, this being a government sanctioned frequency for conducting PECVD work.
  • the plasma is generated with electrodes powered with sufficient power to form a coating on the substrate surface.
  • the plasma is optionally generated at the first phase to deposit a lubricity coating (i) with electrodes supplied with an electric power of from 0.1 to 50 W, optionally from 2 to 30 W, optionally from 2 to 20 W, preferably 4 to 10 W, for example of 5 W; and/or (ii) wherein the ratio of the electrode power to the plasma volume is less than 10 W/ml, optionally is from 5 W/ml to 0.1 W/ml, optionally is from 4 W/ml to 0.1 W/ml, optionally from 2 W/ml to 0.2 W/ml.
  • the power (in Watts) used for PECVD also has an influence on the coating properties.
  • an increase of the power will increase the barrier properties of the coating, and a decrease of the power will increase the lubricity and hydrophobicity of the coating.
  • a power of less than 30 W will lead to a coating which is predominantly a lubricity coating, while a power of more than 30 W will lead to a coating which is predominantly a barrier layer.
  • a further parameter determining the coating properties is the ratio of O 2 (or another oxidizing agent) to the precursor (e.g. organosilicon precursor) in the gaseous reactant used for generating the plasma.
  • O 2 or another oxidizing agent
  • the precursor e.g. organosilicon precursor
  • an increase of the O 2 ratio in the gaseous reactant will increase the barrier properties of the coating, and a decrease of the O 2 ratio will increase the lubricity and hydrophobicity of the coating.
  • O 2 is optionally present in a volume-volume ratio to the gaseous reactant of from 0:1 to 5:1, optionally from 0:1 to 1:1, even optionally from 0:1 to 0.5:1 or even from 0:1 to 0.1:1.
  • the gaseous reactant should comprise less than 1 vol % O 2 , for example less than 0.5 vol % O 2 , and optionally is O 2 -free. The same applies to a hydrophobic layer.
  • the two-phase PECVD process of the present invention may be utilized to coat or treat outer surfaces, in accordance with at least one embodiment of the present invention, such as the outer surface of an object.
  • the object can also include a vessel.
  • the two-phase PECVD process may be utilized to coat the outer surface of a vessel, such as vial, syringe, cartridge, multi-well plate, bag, or tube.
  • the two-phase PECVD process may be utilized to coat a surface, such as the outer surface, of an object for such products, such as the outer surface of a plunger, stopper, or seal.
  • the coating process may utilize a product or object holder or fixture to enable the coating or treatment of the desired surface(s).
  • FIGS. 11A and 11B One exemplary holder within a coating chamber 500 useful to coat a surface of a vessel or object, in accordance with at least one embodiment of the present invention, shown in FIGS. 11A and 11B .
  • FIG. 11A shows an isometric view of the object holder within the chamber 500
  • FIG. 11B shows a front view of the object holder within the chamber 500 .
  • the holder within the chamber 500 may be utilized to coat or treat a surface of an object, such as coating an outer surface of a plunger useful in syringes.
  • Such syringe may optionally contain the same coating, enabled by the two-phase PECVD process of the present invention, on its interior surface; thereby enabling the surface interaction between the plunger and the syringe to have the same coating.
  • Other such holders within a chamber can similarly be utilized to enable coating of various interior or exterior surfaces of vessels and objects, as would be readily appreciated by one having ordinary skill in the art of holders or fixtures for processing of vessels and objects.
  • the substrate optionally can be injection molded, blow molded, or otherwise formed from a polymer selected from the group consisting of a polycarbonate, an olefin polymer, for example a cyclic olefin copolymer (COC), a cyclic olefin polymer (COP), or polypropylene, and preferably COP; a polyester, for example polyethylene terephthalate or polyethylene naphthalate; polylactic acid; a polymethylmethacrylate; or a combination of any two or more of these.
  • a polymer selected from the group consisting of a polycarbonate, an olefin polymer, for example a cyclic olefin copolymer (COC), a cyclic olefin polymer (COP), or polypropylene, and preferably COP; a polyester, for example polyethylene terephthalate or polyethylene naphthalate; polylactic acid; a polymethylmethacrylate; or a combination of any
  • the vessel can be made of glass or a polymer material such as polyester, for example polyethylene terephthalate (PET), a cyclic olefin copolymer (COC), an olefin such as polypropylene, or other materials.
  • PET polyethylene terephthalate
  • COC cyclic olefin copolymer
  • an olefin such as polypropylene
  • Applying a lubricity layer by PECVD can avoid or reduce the need to coat the vessel wall or closure with a sprayed, dipped, or otherwise applied organosilicon or other lubricant that commonly is applied in a far larger quantity than would be deposited by a PECVD process.
  • the vessel 80 can also be made, for example of glass of any type used in medical or laboratory applications, such as soda-lime glass, borosilicate glass, or other glass formulations. Other vessels having any shape or size, made of any material, are also contemplated for use in the system.
  • One function of coating a glass vessel can be to reduce the ingress of ions in the glass, either intentionally or as impurities, for example sodium, calcium, or others, from the glass to the contents of the vessel, such as a reagent or blood in an evacuated blood collection tube.
  • Another function of coating a glass vessel in whole or in part, such as selectively at surfaces contacted in sliding relation to other parts, is to provide lubricity to the coating, for example to ease the insertion or removal of a stopper or passage of a sliding element such as a piston in a syringe. Still another reason to coat a glass vessel is to prevent a reagent or intended sample for the vessel, such as blood, from sticking to the wall of the vessel or an increase in the rate of coagulation of the blood in contact with the wall of the vessel.
  • a related embodiment is a vessel made of plastic, in which the barrier coating is made of soda lime glass, borosilicate glass, or another type of glass.
  • the container size optionally can be from 0.5 to 10 mL, alternatively from 1 to 3 mL, alternatively from 6 to 10 mL.
  • One optional type of vessel 268 is a syringe including a plunger, a syringe barrel, and a lubricity coating as defined above on either one or both of these syringe parts, preferably on the inside wall of the syringe barrel.
  • the syringe barrel includes a barrel having an interior surface slidably receiving the plunger.
  • the lubricity coating may be disposed on the interior surface of the syringe barrel, or on the plunger surface contacting the barrel, or on both surfaces. The lubricity coating is effective to reduce the breakout force or the plunger sliding force necessary to move the plunger within the barrel.
  • the syringe optionally further includes a staked needle.
  • the needle is hollow with a typical size ranging from 18-29 gauge.
  • the syringe barrel has an interior surface slidably receiving the plunger.
  • the staked needle may be affixed to the syringe during the injection molding of the syringe or may be assembled to the formed syringe using an adhesive.
  • a cover is placed over the staked needle to seal the syringe assembly. The syringe assembly must be sealed so that a vacuum can be maintained within the syringe to enable the PECVD coating process.
  • the syringe can comprise a Luer fitting at its front end.
  • the syringe barrel has an interior surface slidably receiving the plunger.
  • the Luer fitting includes a Luer taper having an internal passage defined by an internal surface.
  • the Luer fitting optionally can be formed as a separate piece from the syringe barrel and joined to the syringe barrel by a coupling.
  • a plunger for a syringe including a piston, and a push rod.
  • the piston has a front face, a generally cylindrical side face, and a back portion, the side face being configured to movably seat within a syringe barrel.
  • the plunger has a lubricity coating according to the present invention on its side face.
  • the push rod engages the back portion of the piston and is configured for advancing the piston in a syringe barrel.
  • the plunger may additionally comprise a SiO x barrier coating, in which x is from 1.5 to 2.9 as measured by XPS
  • a further aspect of the invention is a vessel with just one opening, which can be, for example, a vessel for collecting or storing a compound or composition.
  • a vessel is in a specific aspect a tube, e.g. a sample collecting tube, e.g., a blood collecting tube.
  • a tube may be closed with a closure, e.g. a cap or stopper.
  • Such cap or stopper may comprise a lubricity coating according to the present invention on its surface which is in contact with the tube, and/or it may contain a passivating coating according to the present invention on its surface facing the lumen of the tube.
  • a stopper or a part thereof may be made from an elastomeric material.
  • a further particular aspect of the invention is a syringe barrel coated with the lubricity coating as defined in the preceding paragraph.
  • a precursor is included in the gas feed provided to the PECVD apparatus.
  • the precursor is an organosilicon compound (in the following also designated as “organosilicon precursor”), more preferably an organosilicon compound selected from the group consisting of a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, an alkyl trimethoxysilane, an aza analogue of any of these precursors (i.e. a linear silazane, a monocyclic silazane, a polycyclic silazane, a polysilsesquioxazane), and a combination of any two or more of these precursors.
  • the precursor is applied to a substrate under conditions effective to form a coating by PECVD.
  • the precursor is thus polymerized, crosslinked, partially or fully oxidized, or any combination of these.
  • the organosilicon precursor optionally can include a linear or monocyclic siloxane, optionally comprising or consisting essentially of octamethylcyclotetrasiloxane (OMCTS), tetramethylcyclotetrasiloxane (TMCTS), hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), or a combination of two or more of these.
  • OCTS octamethylcyclotetrasiloxane
  • TCTS tetramethylcyclotetrasiloxane
  • HMDSO hexamethyldisiloxane
  • TMDSO tetramethyldisiloxane
  • the oxidizing gas can comprise or consist of air, oxygen (O 2 and/or O 3 , the latter commonly known as ozone), nitrous oxide, or any other gas that oxidizes the precursor during PECVD at the conditions employed.
  • the oxidizing gas comprises about 1 standard volume of oxygen.
  • the gaseous reactant or process gas can be at least substantially free of nitrogen.
  • O 2 optionally can be present, preferably in a volume-volume ratio to the organosilicon precursor of from 0:1 to 2:1, optionally from 0:1 to 0.5:1, optionally from 0.01:1 to 1:1, optionally from 0.01:1 to 0.5:1, optionally from 0.1:1 to 1:1.
  • Ar optionally can be present as the inert gas.
  • the gas optionally can be from 1 to 6 standard volumes of the organosilicon precursor, from 1 to 100 standard volumes of the inert gas, and from 0.1 to 2 standard volumes of O 2 .
  • both Ar and O 2 optionally can be present.
  • the method of the invention may comprise the application of one or more coatings made by PECVD from the same or different organosilicon precursors under the same or different reaction conditions.
  • a syringe may first be coated with an SiO x barrier coating using HMDSO as organosilicon precursor, and subsequently with a lubricity coating using OMCTS as organosilicon precursor.
  • OMCTS is one of the highest molecular weight and boiling point organosiloxanes that can still be vaporized and delivered inside the syringe under a partial vacuum.
  • cross-linking is critical to balancing plunger force and subvisible particulates. Too much cross-linking results in a dense coating free of low molecular weight siloxane oligomers and oil droplets, but has no lubrication characteristics. Too little cross-linking results in a loosely networked oil with excellent lubrication, but many siloxane oligomers that can form sub-visible droplets.
  • the extent of cross-link density of the plasma lubricant can be indirectly characterized by Fourier Transform infra-red (FTIR).
  • a gaseous reactant or process gas can be employed having a standard volume ratio of, for example when a lubricity coating is prepared:
  • the gas feed comprises air, oxygen, nitrogen, carbon dioxide, ozone, hydrogen peroxide, any noble gas or any combination of two or more of the above.
  • the gas feed comprises the gases in absence of organosiloxane precursors in the second phase.
  • This is a crosslinking step wherein the lubricity coating deposited in the first phase is treated with higher electromagnetic power without deposition of coating in the second phase. Therefore, no organosiloxane precursors are needed in this phase.
  • PECVD may be carried out at any suitable pressure or vacuum level.
  • the process pressure optionally can be from 0.001 to 100 Torr (from 0.13 Pa to 13,000 Pa), optionally from 0.01 to 10 Torr (from 1.3 to 1300 Pa), optionally from 0.1 to 10 Torr (from 13 to 1300 Pa).
  • the plasma optionally can be generated with microwave energy or RF energy.
  • the plasma optionally can be generated with electrodes powered at a radio frequency, preferably at a frequency of from 10 kHz to less than 300 MHz, more preferably of from 1 to 50 MHz, even more preferably of from 10 to 15 MHz, most preferably at 13.56 MHz.
  • the ratio of the electrode power to the plasma volume for the first pulse optionally can be equal to or more than 1 W/ml, preferably is from 2 W/ml to 50 W/ml, more preferably is from 3 W/ml to 10 W/ml.
  • the first pulse optionally can be applied for 0.1 to 5 seconds, alternatively 0.5 to 3 seconds, alternatively 0.75 to 1.5 seconds.
  • the first phase energy level optionally can be applied in at least two pulses.
  • the second phase electromagnetic energy applied to crosslink the lubricity layer which is deposited in the first phase is higher than the energy in the first phase.
  • the energy level in the second phase optionally can be 5 W to 100 W, preferably 20 W to 70 W, most preferably 30 W to 50 W.
  • the plasma-forming energy optionally can be applied in the first phase at a first energy level, followed by further treatment in a second phase at a second energy level.
  • the second energy level is higher than the first energy level.
  • the vessel can be, for example, a syringe barrel, cartridge, or vial.
  • the vessel has a thermoplastic wall having an interior surface enclosing at least a portion of the lumen, an exterior surface, and a coating set on at least one of the interior surface and the exterior surface of the wall.
  • the coating set can include at least one of a tie coating or layer, a barrier coating or layer or a pH protective coating or layer, and a lubricity coating or layer of the current invention.
  • the tie coating or layer can be formed on the interior surface or the exterior surface. It has the composition SiO x C y H z in which x is from about 0.5 to about 2.4 as measured by X-ray photoelectron spectroscopy (XPS), y is from about 0.6 to about 3 as measured by XPS, and z is from about 2 to about 9 as measured by at least one of Rutherford backscattering spectrometry (RBS) or hydrogen forward scattering (HFS).
  • XPS X-ray photoelectron spectroscopy
  • y is from about 0.6 to about 3 as measured by XPS
  • z is from about 2 to about 9 as measured by at least one of Rutherford backscattering spectrometry (RBS) or hydrogen forward scattering (HFS).
  • RBS Rutherford backscattering spectrometry
  • HFS hydrogen forward scattering
  • the barrier coating or layer has the composition SiO x , in which x is from about 1.5 to about 2.9 as measured by XPS.
  • the barrier coating or layer has a facing surface facing toward the opposed surface of the tie coating or layer (if present) and an opposed surface facing away from the tie coating or layer (if present).
  • the pH protective coating or layer if present, has the composition SiO x C y H z , in which x is from about 0.5 to about 2.4 as measured by XPS, y is from about 0.6 to about 3 as measured by XPS, and z is from about 2 to about 9 as measured by at least one of RBS or HFS.
  • the pH protective coating or layer if present, has a facing surface facing toward the opposed surface of the barrier layer (if present) and an opposed surface facing away from the barrier layer (if present).
  • the contemplated method optionally includes a step for preparing a barrier coating or other optional coating set 285 on the substrate before the lubricity coating 286 is applied.
  • the additional step optionally includes introducing a gas comprising an organosilicon precursor and O 2 in the vicinity of the substrate surface and generating plasma from the gas, thus forming an SiO x barrier coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD).
  • PECVD plasma enhanced chemical vapor deposition
  • the plasma can be generated with electrodes powered with sufficient power to form a SiO x barrier coating on the substrate surface.
  • the electrodes optionally are supplied with an electric power of from 8 to 500 W, preferably from 20 to 400 W, more preferably from 35 to 350 W, even more preferably of from 44 to 300 W, most preferably of from 44 to 70 W.
  • the O 2 optionally can be present in a volume:volume ratio of from 1:1 to 100:1 in relation to the silicon containing precursor, preferably in a ratio of from 5:1 to 30:1, more preferably in a ratio of from 10:1 to 20:1, even more preferably in a ratio of 15:1.
  • the lubricity layer of the current invention is applied on a surface coated using organosiloxane as the gas precursor.
  • a graded composite can be separate layers of a lubricity layer or coating and/or hydrophobic layer or coating and SiO x with a transition or interface of intermediate composition between them, or separate layers of a lubricity layer or coating and/or hydrophobic layer or coating and SiO x with an intermediate distinct layer or coating of intermediate composition between them, or a single layer or coating that changes continuously or in steps from a composition of a lubricity layer or coating and/or hydrophobic layer or coating to a composition more like SiO x , going through the coating in a normal direction.
  • the grade in the graded composite can go in either direction.
  • a lubricity layer or coating and/or hydrophobic layer or coating can be applied directly to the substrate and graduate to a composition further from the surface of SiO x .
  • the composition of SiO x can be applied directly to the substrate and graduate to a composition further from the surface of a lubricity layer or coating and/or hydrophobic layer.
  • a graduated coating is particularly contemplated if a coating of one composition is better for adhering to the substrate than the other, in which case the better-adhering composition can, for example, be applied directly to the substrate.
  • the more distant portions of the graded coating can be less compatible with the substrate than the adjacent portions of the graded coating, since at any point the coating is changing gradually in properties, so adjacent portions at nearly the same depth of the coating have nearly identical composition, and more widely physically separated portions at substantially different depths can have more diverse properties. It is also contemplated that a coating portion that forms a better barrier against transfer of material to or from the substrate can be directly against the substrate, to prevent the more remote coating portion that forms a poorer barrier from being contaminated with the material intended to be barred or impeded by the barrier.
  • the coating instead of being graded, optionally can have sharp transitions between one layer or coating and the next, without a substantial gradient of composition.
  • Such coatings can be made, for example, by providing the gases to produce a layer or coating as a steady state flow in a non-plasma state, then energizing the system with a brief plasma discharge to form a coating on the substrate. If a subsequent coating is to be applied, the gases for the previous coating are cleared out and the gases for the next coating are applied in a steady-state fashion before energizing the plasma and again forming a distinct layer or coating on the surface of the substrate or its outermost previous coating, with little if any gradual transition at the interface.
  • the lubricity layer or coating can be post-cured after the PECVD process.
  • Radiation curing approaches including UV-initiated (free radial or cationic), electron-beam (E-beam), and thermal as described in Development Of Novel Cycloaliphatic Siloxanes For Thermal And UV-Curable Applications (Ruby Chakraborty Dissertation, can 2008 ) be utilized.
  • the lubricity coated container optionally can be further treated by post heating it, optionally at 50 to 110 degrees C., alternatively 80 to 100 degree C., optionally for a time interval of 1 to 72 hours, alternatively 4 to 48 hours, alternatively 8 to 32 hours, alternatively 20 to 30 hours.
  • the post heating step optionally can be carried out under at least partial vacuum, alternatively under a pressure of less than 50 Torr, alternatively under a pressure of less than 10 Torr, optionally under a pressure of less than 5 Torr, alternatively at a pressure of less than 1 Torr.
  • the result of the present treatment can be a coated substrate coated with a lubricity coating.
  • the lubricity coating optionally can have an average thickness of from 1 to 5000 nm, alternatively from 30 to 1000 nm, as another alternative from 100 to 500 nm.
  • the optional SiO x barrier coating or layer of any embodiment optionally can have a thickness of from 20 to 30 nm.
  • the absolute thickness of the lubricity coating at single measurement points can be higher or lower than the range limits of the average thickness, with maximum deviations of preferably +/ ⁇ 50%, more preferably +/ ⁇ 25% and even more preferably +/ ⁇ 15% from the average thickness. However, it typically varies within the thickness ranges given for the average thickness in this description.
  • Uniform plasma means regular plasma that does not include a substantial amount of hollow cathode plasma (which has a higher emission intensity than regular plasma and is manifested as a localized area of higher intensity interrupting the more uniform intensity of the regular plasma).
  • the hollow cathode effect is generated by a pair of conductive surfaces opposing each other with the same negative potential with respect to a common anode. If the spacing is made (depending on the pressure and gas type) such that the space charge sheaths overlap, electrons start to oscillate between the reflecting potentials of the opposite wall sheaths leading to multiple collisions as the electrons are accelerated by the potential gradient across the sheath region. The electrons are confined in the space charge sheath overlap which results in very high ionization and high ion density plasmas. This phenomenon is described as the hollow cathode effect. Those skilled in the art are able to vary the processing conditions, such as the power level and the feed rates or pressure of the gases, to form uniform plasma throughout or to form plasma including various degrees of hollow cathode plasma.
  • the area close to the inlet (for example, the area close to the flange of a syringe) is coated thicker than the area distal to the inlet (for example, the area close to the needle and far from the flange in a syringe).
  • Applicants have found that providing relative axial motion between the vessel and the gas inlet during the coating process allows the deposited lubricity layer to be more evenly distributed along the length of the vessel being coated.
  • Low electromagnetic power may afford higher lubricity properties. However, it tends to give less adhered and less crosslinked coating which potentially leads to high particle count. Applicants found that increasing RF power results in a layer that more strongly adheres to the vessel and a high-power crosslinking treatment affords less particle counts.
  • the inventors also found that providing relative axial motion between the vessel and the gas inlet at the first phase and increasing the RF power at the second phase are able to reduce the number of particles liberated from the lubricity layer while maintain high lubricity properties.
  • relative axial motion between the vessel and the gas inlet and/or low electromagnetic power applied during the first phase combined with increasing RF power/or pressure at the second phase provides lubricity to a greater portion of the container, with less potential for particulate formation.
  • a method for preparing a lubricity coating or layer 286 on a plastic substrate 280 such as the interior surface 254 of a vessel 268 , 80 , for example on its wall 280 is illustrated.
  • a suitable vessel shown in FIGS. 12 and 12A , is a syringe barrel 250 for a medical syringe 252 having an inner surface 254 .
  • Such syringes 252 are sometimes supplied prefilled with saline solution, a pharmaceutical preparation, or the like for use in medical techniques.
  • a syringe barrel 250 as molded commonly can be open at both the back end 256 , to receive a plunger 258 , and at the front end 260 , to receive a hypodermic needle, a nozzle, or tubing for dispensing the contents of the syringe 252 or for receiving material into the syringe 252 .
  • the front end 260 can optionally be capped and the plunger 258 optionally can be fitted in place before the prefilled syringe 252 is used, closing the barrel 250 at both ends.
  • a cap 262 can be installed either for the purpose of processing the syringe barrel 250 or assembled syringe, or to remain in place during storage of the prefilled syringe 252 , up to the time the cap 262 is removed and (optionally) a hypodermic needle or other delivery conduit is fitted on the front end 260 to prepare the syringe 252 for use.
  • the coating method comprises several steps.
  • a vessel 268 is provided having an open end, a closed end, and an interior surface.
  • At least one gaseous reactant is introduced within the vessel 268 .
  • Plasma is formed within the vessel 268 under conditions effective to form a reaction product of the reactant, i.e. a coating, on the interior surface of the vessel 268 .
  • the electric power at this phase is the second power and the pressure at this phase is the second pressure.
  • the second power is higher than the first power. Exemplary coating parameters related to this step are shown below.
  • the testing can be carried out to measure the initial force Fi and the maintenance force Fm required to start and continue to move the plungers in the barrels of syringes.
  • the plungers used for testing are Datwyler Omniflex or other suitable plungers. INSTRON compression testing instrument is used for the testing.
  • the testing procedures are as follows:
  • the plungers are inserted into the syringes obtained for testing using the plunger loading instrument. Plungers are inserted 18 mm into barrel (see FIG. 17 ) before testing, unless otherwise specified. The needle shields are removed prior to testing. The syringes with the plunger are loaded into the compression testing instrument to determine the Fi and Fm.
  • the starting distance between the cross head member of the Instron testing instrument and the end of the plunger rod is about 12.5 mm in Example 4.
  • This protocol applies to the analysis of sub-visible particles in the coated device using Micro Flow Imaging (MFI, i.e. FlowCam).
  • MFI Micro Flow Imaging
  • Particle Free Water Type I water (ultra-pure, with a resistivity of 18.2 M ⁇ ) that has been filtered through a 0.22 ⁇ m pore-size filter can be obtained from a Millipore MilliQ or equivalent water filtration system.
  • the laminar flow hood is on and has been for at least 0.5 hours before attempting to conduct particle analysis.
  • Container analysis is performed using the 10 ⁇ objective and 100 um Standard flow cell.
  • the sample aspiration volume is pre-set to 0.95 mL. Verify that the 10 ⁇ objective is installed and that the edges of the flow cell are aligned to vertical relative to the field of view and that the field of view is centered across the flow cell on the x-y axis. Confirm that the flow cell is clean and there are no contaminants on the outer surface that will effect calibration. If there are carefully clean the outside of the flow cell with a Windex wetted leans paper followed by dry lens paper. Select the 10 ⁇ FC100 um 1mL.cxt context file (Default Context File) from the context tab in Visual Spreadsheet.
  • Setup and focus mode set the flow rate of 0.1 mL/min aspirate either the 10 um NIST bead standard or a pre-shaken (reserved) sample pool containing 1-OMCTS/Si oil droplets starting and stopping the flow while simultaneously adjusting the fine focus knob on the front of the instrument as particles pass through the flow cell.
  • the particle count per mL should be within the specifications listed on the C of A/Label of the Counting Standard. Validex for example, should measure between 900 and 1100 particles/mL (1000 particles/mL+/ ⁇ 10%) in the >5 ⁇ m channel (Note the standard represents a small size range of reference beads and as long as the blank check passed acceptance criteria there is no reason to expect interference effecting the cumulative counts for the reference material).
  • DHR2016-365-0078 Pool 1 Run 1 After the run, be sure to save the run analysis summary (as a .pdf) in a network folder. Perform a single replicate Injection from the same pool comparing the 5 um counts between the two injections. These should compare within +/ ⁇ 20%. After the replicate run aspirate a single volume of PFW through the flow cell in Setup and Focus Mode and dispense the funnel to dryness. Perform analysis of each subsequent pool in duplicate as above followed by a single aspiration funnel volume of PFW water ⁇ 2 mL until all sample pools and/or groups are analyzed. Transcribe a summary report for each group of samples.
  • test protocol may require extraction with a solution other than PFW.
  • the testing solution must be filtered through 0.22 micron pore size filter and tested before use to ensure the particle counts does not exceed the parameters outlined above. Document sample preparation and testing on the designated form.
  • Table 1 describes the coating settings used to produce particle count results in Table 2.
  • Table 2 provides particle count data from a FlowCAM. The syringes were filled with 1 mL of filtered water and shaken horizontally by hand for 10 seconds. The liquid was removed using a pipette and dispensed into the FlowCAM. Table 2 demonstrates that increasing the phase 2 power during the PECVD process significantly reduces sub-visible particle release from the lubricity layer into the liquid contents of a syringe.
  • phase 2 power was high (e.g., 11 W) instead of low (e.g., 2 W)
  • the sub-visible particulate count was significantly less. This indicates that using high phase 2 power adheres the lubricity layer to the vessel better than low phase 2 power.
  • the inventors successfully achieved these goals by axially moving the inlet within the syringe.
  • the gas inlet was moving vertically from the bottom (i.e. the flange side) to the top (i.e. the needle end) of the coated article.
  • the rate of vertical movement of the inlet is determined by 1) the Length of which the inlet needs to travel and 2) the plasma ramp duration.
  • the inlet was moving at a rate of 14.3 mm/sec.
  • Table 3 and FIG. 3 respectively describe coating settings and related results for stationary inlets versus axially moving inlets.
  • FIG. 3 is a graph illustrating the effect of a moving gas inlet on high power OMCTS coating using the coating settings described in Table 3.
  • FIG. 3 shows that moving the gas inlet during PECVD results in substantially uniform and low plunger sliding force compared to syringes in which the lubricity layer was applied while the inlet was stationary.
  • Example 3 Summary of Inlet Low Power Vs. Moving Inlet High Power
  • Table 4 describes coating settings used to produce particle count data presented in Tables 5 and 6, below.
  • Table 5 shows particle count data from a FlowCAM after a relatively gentle preparation in which the syringes were filled with 1 mL of filtered water and inverted 20 times by hand. The liquid was removed using a pipette and dispensed into the FlowCAM.
  • Table 6 shows particle count data from a FlowCAM after a relatively aggressive preparation in which the syringes were filled with 1 mL of filtered water, placed horizontally on a shaker table and shaken for 10 minutes at 1000 RPM. The liquid was then expressed through the needle into the FlowCAM.
  • Tables 5 and 6 show that particle count is dramatically reduced when the gas inlet is moved axially during PECVD and when phase 2 power is high (e.g., 12 W).
  • the invention broadly relates to providing relative axial motion between the vessel and the gas inlet during PECVD application of a lubricity layer. More preferably, such relative motion is provided during the first phase.
  • Example 4 Moving Inlet at 1 st Phase Plus High Power Crosslinking at 2 nd Phase
  • the purpose of this study is to evaluate four processes regarding the resulting plunger force and particle count.
  • Process 1 was a one phase lubricity coating process with low power and static inlet.
  • Process 2 was a one phase lubricity coating process with high power and moving inlet and
  • Process 3 was a two-phase lubricity coating process with low power and moving inlet at the first phase, followed by a post crosslinking step of a moderately higher power (e.g. 10 W) at the second phase.
  • Process 4 was also a two-phase lubricity coating process with low power and moving inlet at the first phase, followed by a post crosslinking step of high power (e.g. 50 W) at the second phase.
  • the closure if applicable, e.g.
  • Processes 1 and 2 were both one phase coating processes while Process 1 employed static inlet with lower power and Process 2 employed moving inlet with higher power.
  • the results show that Process 1 afforded low plunger force but high particle count while Process 2 afforded higher plunger force with lower particle counts. It is contemplated that lower power leads to lower crosslinking density which gives lower plunger force and higher particle counts. While lower plunger force is desired, high particle count is undesirable. How to balance the two conflicting requirements is a long-standing need in the industry.
  • Processes 3 and 4 were both two-phase coating processes, intended to provide a solution to the need by achieving the combination of low plunger force and low particle count.
  • the inventors surmised that moving inlet and low power applied at the 1 st phase gives a uniform lubricity coating and low plunger force and the subsequent high power post-treatment, a crosslinking step, increases crosslinking density to produce low particle count.
  • the main difference between Processes 3 and 4 is the power used at the 2 nd phase.
  • the power at the 2 nd crosslinking phase was dramatically increased from 10 w for Process 3 to 50 w for Process 4.
  • the particle count data obtained by FlowCam show that the particle count was dramatically lowered for Process 4 compared to the rest processes 1-3.
  • Process 4 The most obvious improvement of Process 4 over Process 3 is the substantial decrease of particle count from 14043 (>2 um) to 624 (>2 um) while keeping comparable plunger force. Therefore, the combination of low plunger force and low particle count was obtained through a two-phase lubricity coating process with moving inlet at the first phase and high power post crosslinking at the second phase.
  • the FT-IR spectrum for the coating prepared by Process 4 is shown in FIG. 10 .
  • Table 9 presents the thickness profile data of the coatings generated by Process 1 and Process 4 which exhibit the uniformity of the coatings. The results show that Process 4 affords more uniform lubricity coating along the entire barrel length, from the proximal end to the distal end. Compared to Process 3.
  • a 1-Up platform is a PECVD station where vacuum supply, process gases, and RF power are supplied to one individual article to deposit the coating or coating set on the surface of the coated article.
  • a 4-Up platform is a similar station but in 4 configuration, where the vacuum supply, process gases, and RF power are uniformly split so that each are supplied uniformly to four individual articles.
  • the coating system can be a multiple-Up platform, such as 8-Up, 16-Up, 32-Up etc. Multiple-up coating platform affords economic and other benefits.

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US12091358B2 (en) * 2017-07-05 2024-09-17 SCHOTT Pharma AG & Co., KGaA Glass cylinder for a piston-cylinder assembly with reduced friction, and method for treating a glass cylinder for a piston-cylinder assembly

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